US7863236B2 - Detergent compositions - Google Patents

Detergent compositions Download PDF

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US7863236B2
US7863236B2 US10/548,359 US54835904A US7863236B2 US 7863236 B2 US7863236 B2 US 7863236B2 US 54835904 A US54835904 A US 54835904A US 7863236 B2 US7863236 B2 US 7863236B2
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unsubstituted
alkyl
substituted
formula
compound
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US20060166850A1 (en
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Jürgen Kaschig
Robert Hochberg
Oliver Becherer
Gerhard Merkle
Monika Schaumann
Bernard Schultz
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BASF Corp
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Ciba Specialty Chemicals Corp
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents

Definitions

  • the present invention is directed to detergent compositions containing mixtures of fluorescent whitening agents, as well as to such mixtures of fluorescent whitening agents.
  • a detergent composition D comprising at least one compound of formula (1)
  • X 1 , X 2 , X 3 and X 4 are —N(R 1 )R 2 .
  • C 1 -C 8 alkyl may be methyl, ethyl, n- or isopropyl, n-, sec- or t-butyl, or linear or branched pentyl, hexyl, heptyl or octyl.
  • Preferred are C 1 -C 4 alkyl groups.
  • the alkyl groups are substituted examples of possible substituents are hydroxyl, phenyl, halogen, like fluorine, chlorine or bromine, sulfo, sulfato, carboxy and C 1 -C 4 alkyl, like methoxy and ethoxy.
  • substituents of such alkyl groups are, for example, cyano and —CONH 2 .
  • Preferred substituents are hydroxy, carboxy, cyano, —CONH 2 and phenyl, especially hydroxy, phenyl and carboxy.
  • highly preferred substituents are hydroxy, phenyl and C 1 -C 4 alkoxy, especially hydroxy and phenyl.
  • the alkyl groups can also be uninterrupted or interrupted by —)— (in case of alkyl groups containing two or more carbon atoms).
  • C 5 -C 7 cycloalkyl groups are cyclopentyl and especially cyclohexyl. These groups can be unsubstituted or substituted by, for example, C 1 -C 4 -alkyl, like methyl. Preferred are the corresponding unsubstituted cycloalkyl groups.
  • Halogen may be fluorine, chlorine, bromine or iodine, preferably chlorine.
  • R 1 and R 2 together with the nitrogen atom form a heterocyclic ring such a ring system can be, for example, morpholino, piperidine or pyrrolidine.
  • the heterocyclic ring can be unsubstituted or substituted.
  • An example for such substituents is C 1 -C 4 alkyl, especially methyl.
  • the cation M is preferably an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine.
  • Preferred are Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C 1 -C 4 alkylammonium, mono-, di- or tri-C 2 -C 4 -hydroxyalkylammonium or ammonium that is di- or tri-substituted with a mixture of C 1 -C 4 -alkyl and C 2 -C 4 -hydroxyalkyl groups.
  • Highly preferred is sodium.
  • R 1 and R 2 are preferably independently from each other hydrogen; cyano; methyl; methyl which is substituted by hydroxy, cyano, —CONH 2 , COOH or phenyl, especially by COOH; CH 2 CH 2 OH; unsubstituted or C 1 -C 4 alkyl-substituted C 6 -C 7 cycloalkyl, especially cyclohexyl; or R 1 and R 2 , together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
  • R 1 and R 2 are independently from each other hydrogen; methyl; COOH-substituted methyl; CH 2 CH 2 OH; unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 7 cycloalkyl, or R 1 and R 2 , together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
  • R 1 and R 2 are hydrogen, methyl or —CH 2 CH 2 OH, or R 1 and R 2 , together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring. Most preferred are unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine rings, especially morpholino, formed by R 1 and R 2 together with the nitrogen atom linking them.
  • —N(R 1 )R 2 groups are —NH 2 , —NHCH 3 , —N(CH 3 ) 2 , —NH(CH 2 CH 2 OH), —N(CH 2 CH 2 OH) 2 , —NH(CH 2 COOH), —N(CH 3 )(CH 2 COOH), —NH(CN),
  • X 1 and X 3 have preferably the same meanings.
  • X 2 and X 4 have the same meanings.
  • the four radicals X 1 , X 2 , X 3 and X 4 do not have identical meanings.
  • detergent compositions D comprising at least one compound of formula (1), wherein
  • R 1 and R 2 are independently from each other hydrogen; cyano; methyl which is unsubstituted or substituted by hydroxy, cyano, —CONH 2 , —COOH or phenyl;
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
  • detergent compositions D comprising at least one compound of formula (1), wherein
  • X 1 and X 3 are amino, and
  • X 2 and X 4 are a radical of formula —N(R 1 )R 2 ,
  • detergent compositions D comprising at least one compound of formula (2) wherein
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 4 alkyl or substituted C 1 -C 4 alkyl,
  • R 4 and R 5 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 4 alkyl or substituted C 1 -C 4 alkyl, or
  • NR 4 R 4 and/or NR 6 R 4 form a morpholino ring
  • M is hydrogen or an alkali metal atom, an alkaline earth metal atom, ammonium or a cation formed from an amine.
  • detergent compositions D comprising at least one compound of formula (2) wherein
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 and R 8 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 4 R 4 and/or NR 5 R 6 form a morpholino ring
  • M is hydrogen or an alkali metal atom.
  • detergent compositions D comprising at least one compound of formula (2a)
  • R 3 is hydrogen; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 is unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 4 R 4 forms a morpholino ring
  • M is hydrogen or an alkali metal atom, preferably sodium.
  • An especially preferred detergent composition D comprises at least one compound of formula (1′)
  • R 1 and R 2 are independently from each other hydrogen; unsubstituted or COOH or CN substituted methyl; CH 2 CH 2 OH; unsubstituted or C 1 -C 4 alkyl-substituted cyclopentyl or cyclohexyl, or
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, and
  • the molar ratio of compound (1) or (1′) to compound (2) or (2a) or (2b)-(2f) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5.
  • Compounds of formula (1) may be produced by reacting, under known reaction conditions, cyanuric chloride, successively, in any desired sequence, with each of 4,4-diaminostilbene-2,2′-disulfonic acid, and amino compounds capable of introducing the groups X 1 , X 2 , X 3 and X 4 .
  • cyanuric chloride a compound capable of introducing the groups X 1 , X 2 , X 3 and X 4 .
  • 2 moles of cyanuric chloride are initially reacted with 1 mole of 4,4′-diaminostilbene-2,2′-disulfonic acid and then reacting the intermediate obtained in any order with amino compounds capable of introducing the groups X 1 , X 2 , X 3 and X 4 .
  • the detergent compositions used preferably comprise
  • detergent compositions used comprise
  • an amount of a mixture comprising at least one compound of formula (1) and comprising at least one compound of formula (2) of 0.001-5 wt-%, especially an amount of 0.01-5 wt-% is used. Highly preferred is an amount of 0.05-5 wt-%, especially 0.05 to 2%.
  • amounts given in percent are to be understood as being percent by weight, based on the total weight of the detergent composition, unless otherwise stated.
  • the detergent composition may be formulated as a solid, as an aqueous liquid comprising, e.g., 5-50 wt-%, preferably 10-35 wt-% of water or as a non-aqueous liquid detergent, containing not more than 5 wt-%, preferably 0-1 wt-% of water, and based on a suspension of a builder in a non-ionic surfactant, as described; e.g., in GB-A-2158454.
  • the anionic surfactant component may be, e.g., an alkylbenzenesulfonate, an alkysulfate, an alkylethersulfate, an olefinsulfonate, an alkanesulfonate, a fatty acid salt, an alkyl or alkenyl ether carboxylate or an ⁇ -sulfofatty acid salt or an ester thereof.
  • alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkyl group
  • alkylsulfates having 8 to 18 carbon atoms
  • alkylethersulfates having 8 to 18 carbon atoms
  • fatty acid salts being derived from palm oil or tallow and having 8 to 18 carbon atoms.
  • the average molar number of ethylene oxide added in the alkylethersulfate is preferably 1 to 20, preferably 1 to 10.
  • the salts are preferably derived from an alkaline metal like sodium and potassium, especially sodium.
  • alkali metal sarcosinates of formula R—CO(R 1 )CH 2 COOM 1 in which R is allyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R 1 is C 1 -C 4 alkyl and M 1 is an alkali metal, especially sodium.
  • the nonionic surfactant component may be, e.g., primary and secondary alcohol ethoxylates, especially the C 8 -C 20 aliphatic alcohols ethoxylated with an average of from 1 to 20 moles of ethylene oxide per mole of alcohol, and more especially the C 10 -C 15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol.
  • Non-ethoxylated nonionic surfactants include alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides (glucamide).
  • the total amount of anionic surfactant and nonionic surfactant is preferably 55 wt-%, preferably 5-40 wt-% and more preferably 5-30 wt-%. As to these surfactants it is preferred that the lower limit 110 wt-%, based on the total weight of the detergent composition.
  • the builder component may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly(alkylene phosphonate); or a mixture of these.
  • Preferred silicates are crystalline layered sodium silicates of the formula NaHSi m O 2m+1 .pH 2 O or Na 2 Si m O 2m+1 .pH 2 O in which m is a number from 1.9 to 4 and p is 0 to 20.
  • aluminosilicates are the commercially-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.
  • Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.
  • Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.
  • Preferred organic phosphonates or aminoalkylene poly(alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.
  • the amount of builders is preferably 5-70 wt-%, preferably 5-60 wt-% and more preferably 10-60 wt-%. As to the builders it is preferred that the lower limit is 15 wt-%, especially 20 wt-%, based an the total weight of the detergent composition.
  • Suitable peroxide components include, for example, the organic and inorganic peroxides (like sodium peroxides) known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 5 to 95° C.
  • the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 1, preferably 2 to 20, carbon atoms; in particular peroxyacetic acid or diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest. It is preferred, however, to employ very active inorganic peroxides, such as persulphate, parborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides.
  • the amount of peroxide is preferably 0.5-30 wt-%, preferably 1-20 wt-% and more preferably 1-15 wt-%. in case a peroxide is used, the lower limit is preferably 2 wt-%, especially 5 wt-%, based on the total weight of the detergent composition.
  • the peroxides are preferably activated by the inclusion of a bleach activator.
  • a bleach activator Preferred are such compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
  • Suitable compounds include those that carry O— and/or N-acyl groups having the said number of carbon atoms and/or unsubstituted or substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N -diacetyl-N,N-dimethyl-urea (DDU), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), compounds of formula
  • TAED tetraacetylethylenediamine
  • TAGU tetraacetylglycoluril
  • DDU N,N -diacetyl-N,N-dimethyl-urea
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • R is a sulfonate group, a carboxylic acid group or a carboxylate group, and wherein R′ is linear or branched (C 7 -C 15 )alkyl; also activators that are known under the names SNOBS, SLOBS, NOBS and DOBA, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, and acetylated, optionally N-alkylated, glucamine and gluconolactone.
  • PAG pentaacetylglucose
  • the amount of bleach activator is preferably 0-10 wt-%, preferably 0-8 wt-%.
  • the lower limit is preferably 0.5 wt-%, especially 1 wt-%, based on the total weight of the detergent composiion.
  • Bleaching catalysts which may be added, include, e.g., enzymatic peroxide precursors and/or metal complexes.
  • Preferred metal complexes are manganese, cobalt or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A-0509787.
  • the amount is preferably 0.005 to 2 wt-%, more preferably 0.01 to 2 wt-%, especially 0.05 to 2 wt-%. Highly preferred is an amount of 0.1-2 wt-%, based on the total weight of the detergent composition.
  • bleaching catalysts As examples for bleaching catalysts the following are mentioned:
  • the detergent compositions can optionally contain enzymes. Enzymes can be added to detergent compositions for stain removal.
  • the enzymes usually improve the performance on stains that are either protein- or starch-based, such as those caused by blood, milk, grass or fruit juices.
  • Preferred enzymes are cellulases, proteases, amylases and lipases.
  • Preferred enzymes are cellulases and proteases, especially proteases.
  • Cellulases are enzymes which act on cellulose and its derivatives and hydrolyze them into glucose, celloblose, cellooligosaccharide. Cellulases remove dirt and have the effect of mitigating the roughness to the touch. Examples of enzymes to be used include, but are by no means limited to, the following:
  • the enzymes can optionally be present in the detergent compositions.
  • the enzymes are usually present in an amount of 0.01-5 wt-%, preferably 0.05-5 wt-% and more preferably 0.1-4 wt-%, based on the total weight of the detergent composition.
  • Further preferred additives for the detergent compositions according to the invention are polymers that, during the washing of textiles, inhibit staining caused by dyes in the washing liquor that have been released from the textiles under the washing conditions (dye fixing agents, dye transfer inhibitors).
  • Such polymers are preferably polyvinylpyrrolidones, polyvinylimidazoles or polyvinylpyridine N-oxides which may have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000.
  • Such polymers are usually used in an amount of from 0.01 to 5 wt-%, preferably 0.05 to 5 wt-%, especially 0.1 to 2 wt-%, based on the total weight of the detergent composoition.
  • Preferred polymers are those given in WO-A-02/02865 (aee especially page 1, last paragraph and page 2, first paragraph).
  • the detergent compositions used will usually contain one or more auxillaries such as soil suspending agents, for example sodium carboxymethylcellulose; salts for adjusting the pH, for example alkali or alkaline earth metal silicates; foam regulators, for example soap; salts for adjusting the spray drying and granulating properties, for example sodium sulphate; perfumes; and also, if appropriate, antistatic and softening agents; such as smectite clays; photobleaching agents; pigments; and/or shading agents.
  • auxiliaries can be present in an amount of, for example, 0.1 to 20 wt-%, preferably 0.5 to 10 wt-%, especially 0.5 to 5 wt-%, based on the total weight of the detergent composition.
  • the detergent compositions can take a variety of physical forms induding powder, granular, tablet and liquid forms. Examples thereof are conventional powder heavy-duty detergents, compact and supercompact heavy-duty detergents and tablets, like heavy-duty detergent tablets.
  • One important physical form is the so-called concentrated granular form adapted to be added to a washing machine.
  • compact detergents Of importance are also the so-called compact (or supercompact) detergents.
  • compact detergents In the field of detergent manufacture, a trend has developed recently towards the production of compact detergents, which contain increased amounts of active substance.
  • the compact detergents In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40° C., or even at room temperatures, e.g. at 25° C.
  • Such detergents usually contain only low amounts of fillers or processing aids, like sodium sulfate or sodium chloride.
  • the amount of such fillers is usually 0-10 wt-%, preferably 0-5 wt-%. especially 0-1 wt-%, based on the total weight of the detergent composition.
  • Such detergent compositions usually have a bulk density of 650-1000 g/l, preferably 700-1000 g/l and especially 750-1000 g/l.
  • the detergent compositions can also be present in the form of tablets. Relevant characteristics of tablets are ease of dispensing and convenience in handling. Tablets are the most compact delivery of solid detergents and have a bulk density of, for example, 0.9 to 1.3 kg/liter. To enable fast disintegration laundry detergent tablets generally contain special disintegrants:
  • the tablets can also contain combinations of any of the above disintegrants.
  • the detergent composition may also be formulated as an aqueous liquid comprising 6-50 wt-%, preferably 10-35 wt-% or as a non-aqueous liquid detergent, containing not more than 5 wt-%, preferably 0-1 wt-% of water, based on the total weight of the detergent composition.
  • Non-aqueous liquid detergent compositions can contain other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2-propanediol) can also be used.
  • the compositions may contain from 5 to 90 wt-%, typically 10 to 50 wt-% of such carriers, based on the total weight of the detergent composition.
  • the detergent compositions can also be present as the so-called “unit liquid dose” form.
  • An especially preferred detergent composition comprises
  • R 1 and R 2 are hydrogen; unsubstituted or COOH or CN substituted methyl;
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, and at least one compound of formulae (2b)-(2f)
  • the molar ratio of compound (1) or (1′) to compound (2) or (2a) or (2b)-(2f) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5.
  • the present invention is directed to a detergent composition D′ comprising at least one compound of formula (1)
  • X 1 , X 2, X 3 and X 4 are, independently of each other, —N(R 1 )R 2 ,
  • M is hydrogen or a cation, together with at least one compound of formula (2)
  • R 3 and R 5 independently from each other, are hydrogen; unsubstituted C 1 -C 8 alkyl or substituted C 1 -C 8 alkyl,
  • R 4 and R 8 independently from each other, are hydrogen; unsubstituted phenyl;
  • NR 3 R 4 and/or NR 5 R 6 form an unsubstituted or substituted morpholino ring
  • M is hydrogen or a cation
  • detergent composition contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase.
  • Preferred am detergent compositions D′ comprising at least one compound of formula (1), wherein
  • R 1 and R 2 are independently from each other hydrogen; cyano; methyl which is unsubstituted or substituted by hydroxy, cyano, —CONH 2 , —COOH or phenyl; CH 2 CH 2 OH; unsubstituted or C 1 -C 4 alkyl-substituted C 5 -C 7 cycloalkyl; or
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
  • detergent compositions D′ comprising at least one compound of formula (1), wherein
  • X 1 and X 3 are amino, and
  • X 2 and X 4 are a radical of formula —N((R 1 )R 2 ,
  • detergent composition D′ comprising at least one compound of formula (2), wherein
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted or substituted methyl,
  • R 5 and R 7 independently of each other, are unsubstituted phenyl; unsubstituted or substituted methyl, or
  • NR 3 R 4 and/or NR 6 R 6 form a morpholino ring
  • M is hydrogen or a cation.
  • detergent composition D′ comprising at least one compound of formula (2), wherein
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 and R 6 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 3 R 4 and/or NR 5 R 6 form an unsubstituted or substituted morpholino ring
  • M is hydrogen or a cation.
  • detergent compositions D′ comprising at least one compound of formula (2a)
  • R 3 is hydrogen; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 is unsubstituted phenyl, unsubstituted C 1 -C 2 alkyl, or C 1 C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy or
  • NR 3 R 4 forms a morpholino ring
  • M is hydrogen or an alkali metal atom, preferably sodium.
  • compositions D′ which contain enzymes as well as peroxide, peroxide activator and/or bleaching catalyst.
  • detergent compositions comprising
  • detergent compositions comprising
  • detergent compositions comprising
  • R 1 and R 2 are hydrogen; unsubstituted or COOH or CN substituted methyl;
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, and
  • the molar ratio of compound (1) or (1′) to compound (2) or (2a) or (2b)-(2f) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5.
  • This detergent treatment of textiles can be conducted as a domestic treatment in normal washing machines.
  • the textile fibres treated may be natural or synthetic fibres or mixtures thereof.
  • natural fibres include vegetable fibres such as cotton, viscose, flax, rayon or linen, preferably cotton and animal fibres such as wool, mohair, cashmere, angora and silk, preferably wool.
  • Synthetic fibres include polyester, polyamide and polyacrylonitrile fibres.
  • Preferred textile fibres are cotton, polyamide and wool fibres, especially cotton fibres.
  • textile fibres treated according to the method of the present invention have a density of loss than 1000 g/m 2 , especially less than 500 g/m 2 and most preferred lass than 250 g/m 2 .
  • an amount of 0.01 to 3.0 wt-%, especially 0.05 to 3.0 wt-%, based on the weight of the textile fibre material, of a mixture comprising at least one compound of formula (1) and at least one compound of formula (2) is used.
  • the process is usually conducted in the temperature range of from 5 to 100° C., especially 5 to 60° C.
  • Preferred is a temperature range of 5 to 40° C., especially 5 to 35° C. and more preferably 5 to 30° C.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 11. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accordance with the invention.
  • an elective amount of the detergent composition it is meant e.g., from 20 g to 300 g of product dissolved or dispersed in a wash solution of volume from 5 to 85 liters, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Examples are
  • the liquor ratio is preferably 1:4 to 1:40, especially 1:4 to 1:15. Highly preferred is a liquor ratio of 1:4 to 1:10, especially 1:5 to 1 9.
  • a further object of the present invention is to provide a process for the domestic washing treatment of a textile fibre material (P) wherein the textile fibre material is contacted with an aqueous solution of a detergent composition comprising a mixture comprising at least one compound of formula (1)
  • X 1 , X 2 , X 3 and X 4 are, independently of each other, —N(R 1 )R 2 , wherein
  • M is hydrogen or a cation
  • R 3 and R 5 independently from each other, are hydrogen; unsubstituted C 1 -C 8 alkyl or substituted C 1 -C 6 alkyl,
  • R 4 and R 6 independently from each other, are hydrogen; unsubstituted phenyl; unsubstituted C 1 -C 8 alkyl or substituted C 1 -C 8 alkyl, or
  • NR 3 R 4 and/or NR 5 R 6 form an unsubstituted or substituted morpholino ring
  • M is hydrogen or a cation
  • detergent composition contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase,
  • the temperature of the solution is between 5° C. and 40° C., preferably between 5° C. and 30° C., throughout the process.
  • X 1 , X 2 , X 3 and X 4 are, independently of each other, —N(R 1 )R 2 , wherein
  • M is hydrogen or a cation.
  • X 1 and X 3 are amino, and
  • X 2 and X 4 are a radical of formula —N(R 1 )R 2 ,
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 4 alkyl or substituted C 1 -C 4 alkyl,
  • NR 4 and R 8 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 4 alkyl or substituted C 1 -C 4 alkyl, or
  • NR 3 R 4 and/or NR 5 R 8 form a morpholino ring
  • M is hydrogen or a cation.
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 and R 8 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 3 R 4 and/or NR 5 R 6 form a morpholino ring
  • M is hydrogen or a cation.
  • R 3 is hydrogen; unsubstituted C 1 C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy.
  • R 4 is unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 3 R 4 forms an unsubstituted or substituted morpholino ring
  • M is hydrogen or an alkali metal atom, preferably sodium.
  • R 1 and R 2 independently from each other are hydrogen; unsubstituted or COOH or CN substituted methyl; CH2CH 2 OH; unsubstituted or C 1 -C 4 alkyl-substituted cyclopentyl or cyclohexyl, or
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring, and
  • detergent composition contains at least one enzyme selected from the group consisting of cellulase, protease, amylase and lipase,
  • the temperature of the solution is between 5° C. and 40° C., preferably between 50C and 30° C., throughout the process.
  • an amount of 0.01 to 3.0 wt-%, especially 0.05 to 3.0 wt-%, based on the weight of the textile fibre material, of the mixture comprising at least one compound of formula (1) or (1′) and at least one compound of formula (2), (2a) or (2b)-(2f) is used.
  • the molar ratio of compound (1) or (1′) to compound (2) or (2a) or (2b)-(2f) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5.
  • the mixtures used according to the present invention are particularly advantageous in that they exhibit not only extremely high whitening ability, but, in addition, in many cases highly desirable water solubilities and also possess excellent white aspects in the solid state.
  • a further advantage of the present invention is that the detergent composition delivers improved whiteness performance and fabric feel. Furthermore the mixtures show very good results with respect to exhaustion properties.
  • a further embodiment of the present invention are mixtures M comprising at least one compound of formula (1)
  • X 1 , X 2 , X 3 , and X 4 are, independently of each other, —N(R 1 )R 2 , wherein
  • M is hydrogen or a cation.
  • R 3 and R 5 independently from each other, are hydrogen; unsubstituted C 1 -C 8 alkyl or substituted C 1 -C 8 alkyl,
  • R 4 and R 8 independently from each other, are hydrogen, unsubstituted phyenyl
  • NR 3 R 4 and/or NR 5 R 6 from an unsubstituted or substituted morpholino ring
  • M is hydrogen or a cation.
  • mixtures M comprising at least one compound of formula (1), wherein
  • R 1 and R 2 are independently from each other hydrogen; cyano; methyl which is unsubstituted or substituted by hydroxy, cyano, —CONH 2 , —COOH or phenyl;
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
  • mixtures M comprising at least one compound of formula (1), wherein
  • X 1 and X 3 are amino, and
  • X 2 and X 4 are a radical of formula —N(R 1 )R 2 ,
  • mixtures M comprising at least one compound of formula (1), wherein R 1 and R 2 , together with the nitrogen atom linking them, form an unsubstituted or C 1 - 4 alkyl-substituted morpholino, piperidine or pyrrolidine ring.
  • mixtures M comprising at least one compound of formula (2), wherein
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 4 alkyl or substituted C 1 -C 4 alkyl,
  • R 4 and R 8 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 4 alkyl or substituted C 1 -C 4 alkyl, or
  • NR 3 R 4 and/or NR 5 R 6 form an unsubstituted or substituted morpholino ring
  • M is hydrogen or a cation.
  • mixtures M comprising at least one compound of formula (2), wherein
  • R 3 and R 5 independently of each other, are hydrogen; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 and R 8 independently of each other, are unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 3 R 4 and/or NR 5 R 6 form an unsubstituted or substituted morpholino ring
  • M is hydrogen or a cation.
  • mixtures M comprising at least one compound of formula (2a)
  • R 3 is hydrogen, unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy,
  • R 4 is unsubstituted phenyl; unsubstituted C 1 -C 2 alkyl or C 1 -C 4 alkyl, which is substituted by hydroxy or C 1 -C 4 alkoxy, or
  • NR 3 R 4 forms an unsubstituted or substituted morpholino ring
  • M is hydrogen or an alkali metal atom, preferably sodium.
  • Especially preferred mixtures M are those comprising at least one compound of formula (1′)
  • R 1 and R 2 independently from each other are hydrogen; unsubstituted or COOH or CN substituted methyl; CH 2 CH 2 OH; unsubstituted or C 1 -C 4 alkyl-substituted cyclopentyl or cyclohexyl, or
  • R 1 and R 2 together with the nitrogen atom linking them, form an unsubstituted or C 1 -C 4 alkyl-substituted morphorlino, piperidine or pyrrolidine ring, and
  • the molar ratio of compound (1) or (1′) to compound (2) or (2a) or (2b)-(2f) is usually in the range of from 0.1:99.9 to 99.9:0.1, preferably from 1:99 to 99:1 and more preferably from 5:95 to 95:5.
  • the compounds have the advantage that they are also effective in the presence of active chlorine donors such as, for example, hypochlorite and can be used without substantial lose of the effects in washing baths with non-ionic washing agents, for example alkylphenol polyglycol ethers.
  • non-ionic washing agents for example alkylphenol polyglycol ethers.
  • perborate or peracids and activations for example tetraacetylglycoluril or ethylenediamine-tetraacetic acid are the mixtures of these compounds stable both in pulverulent washing agent and in washing baths. In addition, they impart a brilliant appearance in daylight.
  • the pH increases to a value of 10 and then drops to a lower value, whereby the temperature increases to 10 to 15° C. Then the reaction mixture is warmed to a temperature of 45° C. and held at this temperature for 20 minutes. During heating to 98° C. within 30 minutes a mixture of methylethylketone and water is distilled off; the pH is maintained at a value between 8.5 and 9 by addition of an aqueous sodium hydroxide solution. After no further addition of aqueous sodium hydroxide solution is necessary in order to maintain the pH at a constant value the reaction mixture is cooled to 50° C.
  • a yellowish crystalline precipitate can be filtered off. After drying 29 g of a yellowish product of the compound of formula (103) are obtained.
  • the compound of formula (104a) can be prepared in analogy to the process given in Preparation Example 12, by replacing N,N′-bis-4-morpholino-6-chloro-1,3,5-triazine-2-yl)-4,4′-diaminostilbene-2,2′-disulfonic acid with an equimolar amount of the compound of formula (101).
  • the compound of formula (104b) can be prepared in analogy to the process given in Preparation Example 13, by methylamine with an equimolar amount of dimethylamine.
  • the compound of formula (105) can be prepared in analogy to the process given in Preparation Example 14, by replacing 18 g of an aqueous solution of methylamine (40%) with a corresponding solution containing an equimolar amount of dimethylamine.
  • a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 40° C. over 15 minutes and then rinsed, spindried and ironed at 160° C.
  • washing powders A and B are used (amounts given in the following Tables 2a and 2b are in g):
  • a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 30° C. over 15 minutes and then rinsed, spin-dried and ironed at 160° C.
  • washing powders are used (amounts given in the following Tables 3a and 3b are percent by weight, based on the total weight of the detergent):
  • a wash liquor is prepared by dissolving 0.8 g of a washing powder in 200 ml of tap water. 10 g of bleached cotton fabric is added to the bath and washed at 40° C. over 15 minutes and then rinsed, spin-dried and ironed at 160° C.
  • washing powders A and B are used (amounts given in the following Tables 4a and 4b are in g):

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US20070225184A1 (en) * 2004-04-20 2007-09-27 Ciba Speciality Chemicals Holding Inc. Amphoteric Fluorescent Whitening Agents in Detergent Formulations
WO2014031790A1 (en) 2012-08-23 2014-02-27 Allylix, Inc. Nootkatone as an insecticide and insect repellent
WO2015130669A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015130653A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015148890A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016044200A1 (en) 2014-09-15 2016-03-24 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
WO2016049387A1 (en) 2014-09-26 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016048674A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016048969A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Detergent compositions containing a polyetheramine and an anionic soil release polymer
US9839214B2 (en) 2012-12-18 2017-12-12 Evolva, Inc. Solavetivone and 5-epi-beta-vertivone as pest repellants and pesticides
US9951298B2 (en) 2014-01-20 2018-04-24 The Procter & Gamble Company Fluorescent brightener premix
US20220211130A1 (en) * 2012-02-22 2022-07-07 Paul Anstey Medical/dental/utility glove with anti-fatigue and ergonomic improvement
WO2023017794A1 (ja) 2021-08-10 2023-02-16 株式会社日本触媒 ポリアルキレンオキシド含有化合物

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WO2010048146A1 (en) * 2008-10-20 2010-04-29 Carnegie Mellon University System, method and device for predicting navigational decision-making behavior
CN101429345B (zh) * 2008-12-08 2012-07-18 浙江传化华洋化工有限公司 三嗪二苯乙烯类液体荧光增白剂的制备方法
CN102311657B (zh) * 2011-06-25 2013-12-11 山东大学 具有杀菌作用的低水溶性荧光增白剂及其合成方法与用途
CN102304294B (zh) * 2011-06-25 2014-02-26 山东大学 具有杀菌作用的高水溶性荧光增白剂及其合成方法与用途
CN102924972B (zh) * 2012-11-16 2015-03-18 山西青山化工有限公司 一种高水溶性的二磺酸荧光增白剂组合物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070225184A1 (en) * 2004-04-20 2007-09-27 Ciba Speciality Chemicals Holding Inc. Amphoteric Fluorescent Whitening Agents in Detergent Formulations
US20220211130A1 (en) * 2012-02-22 2022-07-07 Paul Anstey Medical/dental/utility glove with anti-fatigue and ergonomic improvement
US12310437B2 (en) * 2012-02-22 2025-05-27 Paul Anstey Medical/dental/utility glove with anti-fatigue and ergonomic improvement
US20240065352A1 (en) * 2012-02-22 2024-02-29 Paul Anstey Medical/dental/utility glove with anti-fatigue and ergonomic improvement
US11844383B2 (en) * 2012-02-22 2023-12-19 Paul Anstey Medical/dental/utility glove with anti-fatigue and ergonomic improvement
WO2014031790A1 (en) 2012-08-23 2014-02-27 Allylix, Inc. Nootkatone as an insecticide and insect repellent
US9839214B2 (en) 2012-12-18 2017-12-12 Evolva, Inc. Solavetivone and 5-epi-beta-vertivone as pest repellants and pesticides
US10206393B2 (en) 2012-12-18 2019-02-19 Evolva, Inc. Solavetivone and 5-epi-β-vetivone as pest repellants and pesticides
US9951298B2 (en) 2014-01-20 2018-04-24 The Procter & Gamble Company Fluorescent brightener premix
WO2015130669A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
WO2015130653A1 (en) 2014-02-25 2015-09-03 The Procter & Gamble Company A process for making renewable surfactant intermediates and surfactants from fats and oils and products thereof
EP4530332A2 (de) 2014-02-25 2025-04-02 The Procter & Gamble Company Verfahren zur herstellung von erneuerbaren tensidzwischenprodukten und tensiden aus fetten und ölen und produkte daraus
WO2015148890A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016044200A1 (en) 2014-09-15 2016-03-24 The Procter & Gamble Company Detergent compositions containing salts of polyetheramines and polymeric acid
WO2016048969A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Detergent compositions containing a polyetheramine and an anionic soil release polymer
WO2016048674A1 (en) 2014-09-25 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2016049387A1 (en) 2014-09-26 2016-03-31 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
WO2023017794A1 (ja) 2021-08-10 2023-02-16 株式会社日本触媒 ポリアルキレンオキシド含有化合物

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CN1764714A (zh) 2006-04-26

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